Near-Field Electron Energy Loss Spectroscopy in Porous Silicon

First results of an Electron Energy Loss Spectroscopy in the Near Field (NFEELS) mode of n⁺ porous silicon are described here. Sequences of EELS spectra in the low loss energy range (0–30 eV) were recorded, using a scanning transmission electron microscope, as the e-beam was scanned across a nano-hole surrounded by Si platelets. This technique is shown to be very sensitive to spectral and spatial changes in the electromagnetic field distribution outside the surface of nanoparticles, governed by their local nature and shape.     

Combining Upscaling and Downscaling of Methane Emissions from Rice Fields: Methodologies and Preliminary Results

The uncertainty in the methane (CH₄) source strength of rice fields is among the highest of all sources in the global CH₄ budget. Methods to estimate the source strength of rice fields can be divided into two scaling categories: bottom-up (upscaling) and top-down (downscaling). A brief review of upscaling and downscaling methodologies is presented. The combination of upscaling and downscaling methodologies is proposed as a potential method to reduce the uncertainty in the regional CH₄ source strength of rice fields. Some preliminary results based on upscaling and downscaling are presented and the limitations of the approaches are discussed. The first case study focuses on upscaling by using a field-scale model in combination with spatial databases to calculate CH₄ emissions for the island of Java. The reliability of upscaling results is limited by the uncertainty in model input parameters such as soil properties and organic carbon management. Because controlling variables such as harvested rice area may change on relatively short time scales, a land use change model (CLUE) was used to quantify the potential land use changes on Java in the period 1994–2010. The predicted changes were evaluated using the CH₄ emission model. Temporal scaling by coupling land use change models and emission models is necessary to answer policy-related questions on future greenhouse gas emissions. In a downscaling case study, we investigate if inverse modeling can constrain the emissions from rice fields by testing a standard CH₄ from rice scenario and a low CH₄ from rice scenario (80 and 30 Tg CH₄ yr^–1, respectively). The results of this study are not yet conclusive; to obtain fine-resolution CH₄ emission estimates over the Southeast Asian continent, the monitoring network atmospheric mixturing ratios need to be extended and located closer to the continental sources.     

Sintering of Industrial Mullites in the Presence of Magnesia as a Sintering Aid

The sinterability of two industrial mullite powders, in the presence of MgO as a sintering aid, was investigated. A glassy phase, which was generated during preparation, was present in both powders; this glassy phase had a strong influence on sintering, depending on its content, composition, and spatial distribution. MgO promoted sintering in the presence of a liquid phase, both in the as-received materials and in samples washed with HF, in which most of the pre-existing glassy phase was eliminated. Investigations using transmission electron microscopy, coupled with energy-dispersive spectroscopy, as well as dilatometric measurements and X-ray diffraction data, on washed and unwashed materials and on quenched and slow-cooled samples allowed a better understanding of the influence of MgO and the glassy phase on the sintering behavior and the formation of new phases. Most of the phases, in fact, can be explained by using the MgO–Al₂O₃–SiO₂ phase diagram, even in such complex systems.     

Comparison of Urinary Scents of Two Related Mouse Species, <Emphasis Type="Italic">Mus spicilegus</Emphasis> and <Emphasis Type="Italic">Mus domesticus</Emphasis>

Whereas the house mouse (Mus domesticus) has been studied extensively in terms of physiology/behavior and pheromonal attributes, the evolutionarily related mound-building mouse (Mus spicilegus) has received attention only recently due to its divergent behavioral traits related to olfaction. To date, no chemical studies on urinary volatile compounds have been performed on M. spicilegus. The rationale for our investigations was to determine if there are differences in urinary volatiles of intact and castrated M. spicilegus males and to explore further whether this species could utilize the same or structurally similar pheromones as the male house mouse, M. domesticus. The use of capillary gas chromatography/mass spectrometry (GC-MS) together with sorptive stir bar extraction sampling enabled quantitative comparisons between the intact and castrated M. spicilegus urinary profiles. Additionally, through GC-MS and atomic emission (sulfur-selective) detection, we identified qualitative molecular differences between intact M. spicilegus and M. domesticus. A series of volatile and odoriferous lactones and the presence of coumarin were the unique features of M. spicilegus, as was the notable absence of 2-sec-butyl-4,5-dihydrothiazole (a prominent M. domesticus male pheromone) and other sulfur-containing compounds. Castration of M. spicilegus males eliminated several substances, including δ-hexalactone and γ-octalactone, and substantially decreased additional compounds, suggesting their possible role in chemical communication. Some other M. domesticus pheromone components were also found in M. spicilegus urine. These comparative chemical analyses support the notion of metabolic similarities as well as the uniqueness of some volatiles for M. spicilegus, which may have a distinct physiological function in reproduction and behavior.     

Capping Groups Induced Size and Shape Evolution of Magnetite Particles Under Hydrothermal Condition and their Magnetic Properties

Three simple capping molecules (urea, 3-aminopropanol, and polyethylene glycol) with different functional groups (−NH₂ for urea, −NH₂ and −OH for 3-aminopropanol, and −O− for polyethylene glycol) have been designed to prepare magnetite (Fe₃O₄) particles with various shapes. The crystal structure, morphologies, and magnetic properties of the products have been characterized by X-ray diffraction, electron microscopy, and vibrating sample magnetometer. The results indicate that the capping functional groups play a major role in determining the size, shape, and thus magnetic properties of the magnetite nanocrystals. The morphology evolution of the magnetite under the hydrothermal condition is discussed in detail, particularly for the interaction between the various capping groups and surface structure and chemistry of the nanocrystals.     

Silicon Substitution for Aluminum in Calcium Silicate Hydrates

²⁷Al MAS and multiquantum (MQ) MASNMR (magic-angle spinning nuclear magnetic resonance) spectroscopy were used to study the substitution of silicon by aluminum in calcium silicate hydrates (C-S-H), which are the main component of hydrated portland cement. Synthetic C-S-H samples were prepared, and their chemical stability was studied. Two-dimensional 3Q-MASNMR spectra revealed the chemical shift and quadrupolar parameters (delta_iso, nu_Q) that labeled aluminum sites in the C-S-H. Tetrahedral aluminum was observed in the bridging and nonbridging sites of the silicate chains.     

Stress corrosion cracking susceptibility of P285NH and API 5L X65 steel grades in the high-level radioactive waste repository cell concept

Since 2014, the concept developed for the disposal of high-level radioactive waste in the French deep geological repository project Cigéo includes a cement-based grout material. This cement-based grout material will be injected between the casing and the claystone to neutralize the potential acidity resulting from the claystone oxidation induced by the drilling process of the disposal cell. In these conditions of pH (around 10.5) and temperature (90°C, maximum expected during the disposal), the metallic materials could be sensitive to stress corrosion cracking (SCC). In this project, different environments (aerated or deaerated, at room temperature or at 90°C) and synthetic solutions are considered to reproduce the different periods expected during the long life repository. The project is based on electrochemical measurements (polarization curves to define the SCC critical domain of potentials), slow strain rate tensile tests, and long-term immersion for crack initiation and propagation tests.     

High-throughput approach to the catalytic combustion of diesel soot

A methodology for the evaluation of diesel soot oxidation catalysts by high-throughput (HT) screening was developed. The optimal experimental conditions (soot amount, catalyst/soot ratio, type of contact, composition and flow rate of gas reactants) ensuring a reliable and reproducible detection of light-off temperatures in a 16 parallel channels reactor were set up. The temperature profile measured in the catalyst/soot bed under TPO conditions when the exothermic combustion of soot takes place was shown to provide an accurate measurement of the ignition. Its reproducibility and relevance were checked. The results obtained with a reference noble metal free catalyst (La_0.8Cr_0.8Li_0.2O₃ perovskite) agree very well with literature data. Qualitative mechanistic features could be derived from these experiments, stressing the likely limiting step of oxygen transfer from catalyst surface to soot particulates to ignite the soot combustion. Ceria material was shown to be more appropriate than perovskite one. From an HT screening of a large diverse library (over 100 mixed oxides catalysts) under optimized conditions, about 10 new formulations were found to perform better than selected noble metal free reference materials.     

Spark plasma sintering of double-walled carbon nanotubes

Bulk samples of double-walled carbon nanotubes are prepared for the first time. The best spark plasma sintering conditions are (1100 °C, 100 MPa). Raman spectroscopy and scanning electron microscopy show that the nanotubes are undamaged. The density is equal to 1.29 g cm⁻³ and the pores are all below 6 nm in diameter. The electrical conductivity is equal to 1650 S cm⁻¹. The transverse fracture strength is equal to 47 MPa.     

One-line measurement of the residence time distribution in screw extruders

A fluorescence monitoring device was constructed to measure in real time the residence time distribution (RTD) function in screw extruders. Its centerpiece was an optical fiber probe capable of transmitting optical excitation energy to the processed flow stream and detecting the subsequent fluorescence emission. The source of fluorescence emission was an anthracene-bearing substance that was injected to the flow stream as a pulse (tracer) in very small amounts. This device was validated against an off-line ultraviolet spectrophotometer and self-checked as well. In addition to its great sensitivity to fluorescence emission and ease of implementation on an extrusion line, this device could be used to monitor in real time subtle variations of an extrusion operation. The influence of the nature of anthracene-bearing compounds on the measured distribution and the effects of processing parameters on the RTD function were also investigated.